CN114669291A - 一种用于甲烷催化氧化的反蛋白结构催化剂颗粒及其制备方法 - Google Patents
一种用于甲烷催化氧化的反蛋白结构催化剂颗粒及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种用于甲烷催化氧化的反蛋白结构催化剂颗粒，以无机纳米粒子为载体，表面负载催化氧化甲烷的催化剂，具有大孔‑介孔‑微孔的多级孔结构，其粒径范围为50～1000微米；制备方法包括：(1)利用乳液聚合法制备聚合微球；(2)将微球、无机纳米粒子和催化剂前驱体溶解在溶液中成为连续相，油相作为分散相，通过微流控技术，制备微液滴，将所得的微液滴干燥去除溶剂，得到有机无机杂化微球颗粒；(3)将(2)的有机无机杂化微球颗粒煅烧，从而获得反蛋白结构催化剂颗粒；该催化剂颗粒具有反蛋白结构，孔径大，表面负载催化剂，有利于甲烷的催化转化，孔道排列整齐有序可降低物质扩散阻力，为物质的扩散提供最佳流速及更高的效率。
Description
技术领域
本发明涉及一种催化剂，特别涉及一种用于甲烷催化氧化的反蛋白结构催化剂颗粒及其制备方法。
背景技术
甲烷，作为天然气等的主要成分，由于其储量大、价格相对低廉，不仅是化石燃料中最清洁的燃料之一，也是生产大宗化学品的重要C1原料。近年来，天然气产量在化石能源中的占比总体呈增长趋势，整体增长了3.7％。天然气已逐步成为中国清洁能源体系的主体能源之一。因此，天然气资源的合理应用对经济和环境都有着至关重要的作用。然而，大部分天然气资源都分布在人烟稀少的偏远地区，甲烷作为易燃易爆气体，其长途运输有很大的危险性，且经济成本高。与甲烷不同，甲醇在常温下呈液态，不仅是解决能源危机的重要清洁能源之一，也是生产烯烃、二甲醚等精细化学品的重要有机化工原料。因此，将甲烷催化氧化成甲醇等方便运输且具有更高附加值的化学品对于实现甲烷减排及高效利用具有重要意义。
用于甲烷催化氧化的催化剂类型主要包括的是Pt系催化剂、Pd系催化剂、Rh系催化剂、Fe改性沸石催化剂、Cu改性沸石催化剂、改性金属有机框架材料催化剂，这些催化剂载体的微孔孔道限制了反应物分子及产物分子在催化过程中的流通和扩散性能。
发明内容
发明目的：本发明第一目的是提供一种流通、扩散性能好的用于甲烷催化氧化的反蛋白结构催化剂颗粒；本发明的第二目的提供该催化剂的制备方法。
技术方案：本发明所述的催化剂颗粒，以无机纳米粒子为载体，表面负载催化氧化甲烷的催化剂，具有大孔-介孔-微孔的多级孔结构，其粒径范围为50～1000微米。
优选的，所述催化氧化甲烷的催化剂为钯系催化剂、铂系催化剂、铑系催化剂或镧锰基钙钛矿催化剂，能够将甲烷催化氧化为甲醇。
优选的，镧锰基钙钛矿为La0.5Sr0.5MnO3、La0.9Sr0.1MnO3或La0.8Sr0.2MnO3。
优选的，所述无机纳米粒子为二氧化硅、二氧化钛、氧化锆、氧化铈或二氧化钛纳米粒子中的一种。
本发明的用于甲烷催化氧化的反蛋白结构催化剂颗粒的制备方法，包括以下步骤：
(1)利用乳液聚合法制备聚合微球；
(2)将微球、无机纳米粒子和催化剂前驱体溶解在溶液中成为连续相，油相作为分散相，通过微流控乳化法制备微液滴，将所得的微液滴干燥去除溶剂，得到有机无机杂化微球颗粒；
(3)将(2)的有机无机杂化微球颗粒煅烧，从而获得反蛋白结构催化剂颗粒。
优选的，步骤(1)中所述聚合微球为聚苯乙烯或聚甲基丙烯酸甲酯微球，粒径大小范围为0.1～5微米。
所述步骤(2)中，采用微流控乳化法制备单分散微液滴，微液滴尺寸大小可通过调节分散相-连续相的相对流速进行调控，得到粒径为50～1000微米，粒径变异系数小于5％的单分散微液滴。微液滴干燥以及煅烧后不影响其粒径尺寸大小，通过调节微液滴的粒径尺寸，即可确定最后反蛋白结构催化剂颗粒的粒径尺寸。
所述步骤(3)，在煅烧过程中催化氧化甲烷的催化剂前驱体生成相应的催化剂，并且在煅烧过程中去除其中微球模板，从而获得反蛋白结构催化剂颗粒。优选的，所述煅烧温度为400～800℃，煅烧时间为3～4小时。
所述反蛋白结构催化剂颗粒还包括与贵金属纳米粒子前驱体溶液混合均匀，使金属离子还原为金属单质，即可得到负载贵金属纳米粒子的反蛋白结构催化剂颗粒。
有益效果：与现有技术相比，本发明具有如下显著优点：(1)该催化剂表面具有反蛋白石结构，孔径大、孔道排列整齐有序可降低物质扩散阻力，为物质的扩散提供最佳流速及更高的效率；(2)该催化剂颗粒表面的孔结构有序，因而对外易开放，热稳定性强，加热不会收缩闭合；(3)改催化剂表面的孔结构高度有序且相互连接，与传统粉状催化材料相比，易回收；(4)通过微流控技术制备的微球模板大小均一可控，从而实现反蛋白结构催化剂颗粒大小均一可控，适用于多种尺寸微反应填充柱；(5)制备方法简单，易于工业化。
附图说明
图1为反蛋白石结构催化剂颗粒的一般制备流程图；
图2为构建反蛋白石结构催化剂颗粒的胶体光子晶体模板；
图3为实施例1-3的反蛋白石结构催化剂的催化活性图；
图4为实施例1、4和5的反蛋白石结构催化剂的催化活性图。
具体实施方式
下面结合实施例对本发明的技术方案作进一步说明。
实施例1
本发明的用于甲烷催化氧化的反蛋白结构催化剂颗粒，制备方法包括：
(1)采用乳液聚合法制备粒径为200nm的PS(聚苯乙烯)微球(粒径变异系数小于5％)，所得PS微球冻干保存；
(2)称取0.3g PS微球、0.1g SiO2纳米粒子(粒径5nm)、0.31g硝酸镧(0.95mmol)、0.34g硝酸锰(1.90mmol)、0.21g硝酸锶(0.99mmol)分散溶解于由2mL乙二醇、2mL甲醇和6mL去离子水组成的混合溶剂中，得到混合溶液A；将混合溶液A作为分散相，氟油试剂作为连续相，采用微流控乳化法制备单分散微液滴，微液滴尺寸大小可通过调节分散相-连续相的相对流速进行调控，得到粒径大小为200μm、粒径变异系数小于5％的单分散微液滴；将收集的单分散微液滴置于室温条件进行干燥，待溶剂完全挥发后得到有机无机杂化微球A；
(3)将得到的杂化微球A在氮气气氛下进行煅烧(煅烧条件为：800℃，4h)得到多级孔SiO2-La0.5Sr0.5MnO3反蛋白石催化剂颗粒A。
催化剂活性实验在固定床反应器上进行：取0.2g催化剂样品颗粒填入内径为8mm的石英反应管中，两端填入石英棉。反应气组成为：2％CH4，20％O2，剩余78％为平衡气Ar。反应气体的流量通过质量流量计调节，总流速为45mL/min，气体体积空速约为30000h-1，检测反应产物各物质浓度。
实施例2
在实施例1的基础上，在制备获得的反蛋白石催化剂颗粒A表面还引入了Pd纳米粒子；具体步骤如下：
(1)和(2)与实施例1相同；
(3)取0.45g PdCl2、0.30g聚乙烯醇(分子量为104g/mol)分散溶解于10mL去离子水中得到混合溶液B；在冰浴和通入氮气条件下，依次向混合溶液B中加入1g催化剂颗粒A和3gNaBH4，反应30min；
(4)将步骤(3)得到的产物用布氏漏斗抽滤，并用大量去离子水洗涤；洗涤结束后在80℃烘箱中干燥；
(5)将步骤(4)得到的干燥产物在空气气氛下进行煅烧(煅烧条件为：500℃，3h)得到多级孔Pd/SiO2-La0.5Sr0.5MnO3反蛋白石催化剂颗粒B。
催化剂活性实验流程同实施例1。
实施例3
在实施例1的基础上，在制备获得的反蛋白石催化剂颗粒A表面还引入了Au纳米粒子以进一步提高催化效能，具体步骤如下：
(1)和(2)与实施例1相同。
(3)取反蛋白石催化剂颗粒A1g，在其表面滴加1mol/L的醋酸金溶液0.3mL，避光保存30min后，醋酸金渗透到反蛋白石的空隙中；避光条件下自然干燥后用254nm的紫外灯照30min，使Au+还原为单质Au，得到Au/TiO2-La0.5Sr0.5MnO3反蛋白催化剂颗粒C。
催化剂活性实验流程同实施例1。
实施例1-3的反蛋白结构催化剂颗粒的催化活性数据如图3所示，由图中可以看出，负载Pd和Au贵金属的催化剂对甲烷的催化氧化性能几乎相同，优于没有负载贵金属的催化剂。
实施例4
在实施例1的基础上，改变硝酸镧和硝酸锶的比例，具体加入0.56g硝酸镧(1.72mmol)和0.04g硝酸锶(0.19mmol)，其他条件不变，得到SiO2-La0.9Sr0.1MnO3反蛋白催化剂颗粒D。
实施例5
在实施例1的基础上，改变硝酸镧和硝酸锶的比例，具体加入0.50g硝酸镧(1.54mmol)、0.08g硝酸锶(0.38mmol)，其他条件不变，得到SiO2-La0.8Sr0.2MnO3反蛋白催化剂颗粒E。
催化剂活性实验流程同实施例1。
实施例1、4和5的反蛋白结构催化剂颗粒的催化活性数据如图4所示，由图中可以看出，镧锰基钙钛矿催化剂中，镧和锶比例不同，催化效果不同，锶的比例越大，催化效果越好。
Claims (8)
1.一种用于甲烷催化氧化的反蛋白结构催化剂颗粒，其特征在于，以无机纳米粒子为载体，表面负载催化氧化甲烷的催化剂，具有大孔-介孔-微孔的多级孔结构，其粒径范围为50～1000微米。
2.根据权利要求1所述的反蛋白结构催化剂颗粒，其特征在于，所述催化氧化甲烷的催化剂为钯系催化剂、铂系催化剂、铑系催化剂或镧锰基钙钛矿催化剂。
3.根据权利要求2所述的反蛋白结构催化剂颗粒，其特征在于，所述镧锰基钙钛矿为La0.5Sr0.5MnO3、La0.9Sr0.1MnO3或La0.8Sr0.2MnO3。
4.根据权利要求1所述的反蛋白结构催化剂颗粒，其特征在于，所述无机纳米粒子为二氧化硅、二氧化钛、氧化锆、氧化铈或二氧化钛纳米粒子中的一种。
5.一种权利要求1-4任一所述的反蛋白结构催化剂颗粒，其特征在于，包括以下步骤：
(1)利用乳液聚合法制备聚合微球；
(2)将微球、无机纳米粒子和催化剂前驱体溶解在溶液中成为连续相，油相作为分散相，通过微流控乳化法制备微液滴，将所得的微液滴干燥去除溶剂，得到有机无机杂化微球颗粒；
(3)将(2)的有机无机杂化微球颗粒煅烧，从而获得反蛋白结构催化剂颗粒。
6.根据权利要求5所述的反蛋白结构催化剂颗粒，其特征在于，所述聚合微球为聚苯乙烯或聚甲基丙烯酸甲酯微球，粒径大小范围为0.1～5微米。
7.根据权利要求5所述的凝胶的制备方法，其特征在于，所述煅烧温度为400～800℃，煅烧时间为3～4小时。
8.根据权利要求5所述的凝胶的制备方法，其特征在于，所述反蛋白结构催化剂颗粒还包括与贵金属纳米粒子前驱体溶液混合均匀，使金属离子还原为金属单质，得到负载贵金属纳米粒子的反蛋白结构催化剂颗粒。
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